EP0554588B1 - Matériau en feuille ou bande avec des propriétés antistatiques - Google Patents

Matériau en feuille ou bande avec des propriétés antistatiques Download PDF

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Publication number
EP0554588B1
EP0554588B1 EP92204062A EP92204062A EP0554588B1 EP 0554588 B1 EP0554588 B1 EP 0554588B1 EP 92204062 A EP92204062 A EP 92204062A EP 92204062 A EP92204062 A EP 92204062A EP 0554588 B1 EP0554588 B1 EP 0554588B1
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EP
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Prior art keywords
layer
sheet
web material
group
material according
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German (de)
English (en)
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EP0554588A1 (fr
Inventor
Muys c/o Agfa-Gevaert N.V. Bavo
Jonas c/o Agfa-Gevaert N.V. Friedrich
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority claimed from EP19920200230 external-priority patent/EP0553502A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89—Macromolecular substances therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—Macromolecular substances therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein

Definitions

  • the present invention relates to a sheet or web material having antistatic properties, and is particularly but not exclusively concerned with recording materials wherein a hydrophobic resin support carries an antistatic layer and an overlying barrier layer imparting good adherence to a hydrophilic colloid-containing layer, e.g. a light-sensitive gelatin-silver halide emulsion layer.
  • a hydrophobic resin support carries an antistatic layer and an overlying barrier layer imparting good adherence to a hydrophilic colloid-containing layer, e.g. a light-sensitive gelatin-silver halide emulsion layer.
  • hydrophobic resin sheet and web materials of low conductivity readily become electrostatically charged by friction with dielectric materials and/or contact with electrostatically chargeable transport means, e.g. rollers.
  • the charging occurs particularly easily in a relatively dry atmospheric environment.
  • Sheets and webs of hydrophobic resins are commonly used as support element of recording materials. Such materials are subjected to frictional contact with other elements during their manufacture, e.g. during coating or cutting, and during use, e.g. during the recording of information, e.g. with a step-and-repeat or movie camera or - in the case of silver halide photographic materials - during image-processing or image projection.
  • an antistatic layer containing said ionic conductive polymers is moisture dependent and is lowered considerably by treatment with an acidic photographic processing liquid, e.g. an acidic photographic fixing liquid or stop bath.
  • an acidic photographic processing liquid e.g. an acidic photographic fixing liquid or stop bath.
  • Substances having electronic conductivity instead of ionic conductivity have a conductivity independent from relative humidity and changes in pH whereby they are particularly suited for use in the production of antistatic layers with permanent and reproducible conductivity.
  • WO 91/02289 discloses a photographic support material comprising a support having thereon an antistatic layer comprising vanadium pentoxide, characterized in that said support material additionally includes a barrier layer which overlies said antistatic layer and is comprised of a latex polymer having hydrophilic functionality.
  • an overcoat layer that may serve as an outermost layer.
  • a hydrophobic resin support e.g. polyethylene terephthalate resin support or paper support coated with a hydrophobic resin layer carrying a transparent antistatic layer containing an electrically conductive polymer having electronic conductivity, e.g. a conductive polythiophene, which by a barrier layer for said polymer(s) is adhered to an adjacent hydrophilic colloid layer, e.
  • the polythiophenes get positive charges by the oxidative polymerization, the location and number of said charges is not determinable with certainty and therefore they are not mentioned in the general formula of the repeating units of the polythiophene polymer.
  • Oxidizing agents suitable for the oxidative polymerization of pyrrole are described, for example, in J. Am. Soc. 85 , 454 (1963). Inexpensive and easy-to-handle oxidizing agents are preferred such as iron(III) salts, e.g. FeCl 3 , Fe(ClO 4 ) 3 and the iron(III) salts of organic acids and inorganic acids containing organic residues, likewise H 2 O 2 , K 2 Cr 2 O 7 , alkali or ammonium persulfates, alkali perborates, potassium permanganate and copper salts such as copper tetrafluoroborate.
  • iron(III) salts e.g. FeCl 3 , Fe(ClO 4 ) 3 and the iron(III) salts of organic acids and inorganic acids containing organic residues, likewise H 2 O 2 , K 2 Cr 2 O 7 , alkali or ammonium persulfates, alkali perborates, potassium per
  • the thiophenes corresponding to the above general formula (II) are dissolved or emulsified in an organic solvent or preferably in water and the resulting solution or emulsion is stirred at the envisaged polymerization temperature until the polymerization reaction is completed.
  • aqueous polythiophene dispersions are obtained having a solids content of 0.5 to 55% by weight and preferably of 1 to 10% by weight.
  • the polymerization time may be between a few minutes and 30 hours, depending on the size of the batch, the polymerization temperature and the kind of oxidizing agent.
  • the stability of the obtained polythiophene dispersion may be improved during and/or after the polymerization by the addition of dispersing agents, e.g. anionic surface active agents such as dodecyl sulfonate, alkylaryl polyether sulfonates described in United States patent 3,525,621.
  • the size of the polymer particles in the coating dispersion is in the range of from 5 nm to 1 ⁇ m, preferably in the range of 40 to 400 nm.
  • Suitable polymeric polyanion compounds for use in the presence of said polythiophenes are provided by acidic polymers in free acid or neutralized form.
  • the acidic polymers are preferably polymeric carboxylic or sulphonic acids. Examples of such polymeric acids are : polymers containing repeating units selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid and styrene sulfonic acid or mixtures thereof.
  • the anionic (acidic) polymers used in conjunction with the dispersed polythiophene polymer have preferably a content of anionic groups of more than 2% by weight with respect to said polymer compounds to ensure sufficient stability of the dispersion.
  • the polymeric polyanion compounds may consist of straight-chain, branched chain or crosslinked polymers.
  • Cross-linked polymeric polyanion compounds with a high amount of acidic groups are swellable in water and are named microgels.
  • microgels are disclosed e.g. in US-P 4,301,240, US-P 4,677,050 and US-P 4,147,550.
  • the molecular weight of the polymeric polyanion compounds being polyacids is preferably in the range from 1,000 to 2,000,000 and more preferably in the range from 2,000 to 500,000.
  • Polyacids within the above criteria are commercially available, for example polystyrene sulfonic acids and polyacrylic acids, or may be produced by known methods (ref. e.g. Houben-Weyl, Methoden der Organischen Chemie, Vol. E20, Makromolekulare Stoffe, Mol 2, (1987), pp. 141 et seq.).
  • free polymeric polyacids applied in conjunction with the polythiophenes it is possible to use mixtures of alkali salts of said polyacids and non-neutralized polyacids, optionally in the presence of monoacids.
  • Free acid groups of the polyanionic polymer may be allowed to react with an inorganic base, e.g. with sodium hydroxide, to obtain a neutral polymer dispersion before coating.
  • the weight ratio of polythiophene polymer to polymeric polyanion compound(s) can vary widely, for example from about 50/50 to 15/85.
  • a film-forming latex e.g. on the basis of co(vinylidene chloride-methyl acrylateitaconic acid), and/or a water-soluble polymeric colloid binder, e.g. polyvinyl alcohol or gelatin, may be added together with a therefor suited hardening agent.
  • a film-forming latex e.g. on the basis of co(vinylidene chloride-methyl acrylateitaconic acid), and/or a water-soluble polymeric colloid binder, e.g. polyvinyl alcohol or gelatin, may be added together with a therefor suited hardening agent.
  • a surface active agent may be added to the coating composition for improving the spreading of the antistatic layer.
  • anionic as well as non-ionic wetting agents may be used, e.g. a C 12 -C 18 alkylphenol polyethyleneoxide ether such as dodecylphenol polyethylene oxide ether, p-nonyl phenoxy polyglycidol, iso-octyl-phenylene-(O-CH 2 -CH 2 ) 8 -O-CH 2 -COOH sold under the tradename AKYPO OP80 by CHEMY, the Netherlands, or saponine.
  • AKYPO OP80 by CHEMY, the Netherlands
  • saponine saponine.
  • any solvent and water is removed by evaporation which may proceed at room temperature or at elevated temperature, e.g. in the range of 40 to 140°C.
  • the thickness of the antistatic layer is e.g. from 0.001 to 1 ⁇ m, depending on the desired conductivity and transparency of the antistatic coating.
  • the optical density of the antistatic layer is preferably not more than 0.02 measured in the light range of 360 to 630 nm by MACBETH TD 904 densitometer.
  • Useful coverages of solids of the antistatic layer are in the range from 0.001 to 0.3 g/m 2 .
  • Suitable latex polymers for use in the barrier layer used according to the present invention are copolymers of (1) one or more polymerizable monomers selected from the group consisting of styrene, vinylidene chloride, acrylonitrile, alkyl acrylates and alkyl methacrylates with (2) one or more substituted polymerizable monomers selected from the group consisting of styrenes, alkyl acrylates and alkyl methacrylates that have been substituted with a hydrophilic functional group such as an aminoalkyl salt group, an hydroxyalkyl group or carboxylic acid group.
  • a hydrophilic functional group such as an aminoalkyl salt group, an hydroxyalkyl group or carboxylic acid group.
  • group (I) comonomers are : ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.
  • Preferred latex polymers for use in said barrier layer are copolymers of unsaturated carboxylic acids with vinylidene chloride , acrylonitrile, (meth)acrylate monomers, styrene and mixtures thereof. Preference is given to latex polymers containing at least 50 mol % vinylidene chloride repeating units and repeating units with carboxyl functional groups, e.g. itaconic acid and acrylic acid groups.
  • the barrier layer composition may also comprise a monomeric coalescing material, e.g. ethylene carbonate in an amount of 5 to 30 % by weight of the latex polymer.
  • a monomeric coalescing material e.g. ethylene carbonate in an amount of 5 to 30 % by weight of the latex polymer.
  • Particularly preferred latex polymers for forming said overlying barrier layer are terpolymers of vinylidene/methyl (meth)acrylate/itaconic acid containing 70 to 90 mol % vinylidene chloride, 5 to 25 mol % methyl (meth)acrylate and 1 to 10 mole % itaconic acid.
  • the barrier layer is coated at a dry weight coverage of from about 100 to about 3,000 milligrams per m 2 .
  • antistatic layer/barrier layer assemblage it is possible to reduce the surface resistance of a resin sheet or web material to a value lower than 10 10 ohm/square at relative humidity (R.H.) of 30 %.
  • the surface resistance expressed in ohm/square (ohm/sq.) of the above defined antistatic layer is measured according to test procedure A as follows :
  • the resistance of the layer assemblage is measured contact-less by arranging it between capacitor plates making part of a RC-circuit differentiator network.
  • the dimensions of the measurement cell are chosen in such a way that relying on the known capacitor value (C) it is possible to calculate from the measured RC-value the electrical resistance of the layer assemblage.
  • the discharge duration to the value 1/e of the original voltage and charge in the series resistance (R) and capacitor (C) circuit is expressed in milliseconds (msec). The lower that value the better the antistatic character of the applied antistatic layer.
  • a web or sheet according to the invention can incorporate more than one antistatic layer.
  • An important use of the above defined antistatic coating is in the manufacture of photographic silver halide emulsion materials having a hydrophobic resin support or hydrophobic resin coated paper support.
  • Hydrophobic resin supports useful in the manufacture of photographic silver halide emulsion materials are well known to those skilled in the art and are made e.g. of polyester, polystyrene, polyvinyl chloride or polycarbonate, preference being given to polyethylene terephthalate.
  • a preferred resin coated paper support is a poly-Alpha-olefin coated paper support such as a polyethylene coated paper support.
  • the antistatic layer is present at the support side free from silver halide emulsion layer(s) and is separated by said barrier layer from a hydrophilic colloid anti-curl layer substantially equalizing the tension exerted on the front and rear side of the photographic material after wet processing and drying.
  • That anti-curl layer e.g. gelatin containing layer may be hardened to some extent to reduce the take up of water and to improve its abrasion resistance. Suitable hardening agents therefor are described e.g. in The Theory of the Photographic Process edited by T.H. James, 4th ed. Macmillan Publishing Co., Inc. New York, p. 77-87.
  • composition of silver halide emulsion layers reference is made e.g. to Research Disclosure 17,643 of December 1978 and Research Disclosure 307,105 of November 1989.
  • a silver halide photographic material wherein onto said barrier layer at the side opposite the side coated with the silver halide emulsion layer(s) an antihalation layer containing one or more pigments in admixture with a hydrophilic colloid binder, e.g. gelatin, is applied.
  • a hydrophilic colloid binder e.g. gelatin
  • the antireflection substance used in the antihalation coating e.g. carbon black, may itself have antistatic properties.
  • the antistatic layer/barrier layer assemblage may be used in non-photosensitive recording materials serving as image-receiving material in the silver complex diffusion transfer process as described e.g. in the book "Photographic Silver Halide Diffusion Processes” by André Rott and Edith Weyde - The Focal Press London and New York (1972) or in a dye diffusion transfer process as described e.g. by C. Van de Sande in Angew. Chem. Int. Ed. Engl. 22 , (1983) p. 191-209.
  • a photographic silver halide emulsion layer material having an antistatic layer/barrier layer assemblage as defined above, problems caused by static charges can be avoided or substantially reduced.
  • the formation of static charges by contact of a silver halide emulsion layer face with the rear side of the recording material or caused by friction with substances such as rubber and hydrophobic polymeric binder, e.g. the binder constituent of phosphor screens used as X-ray intensifying screens can be markedly reduced by employing the antistatic layer/covering layer assemblage in accordance with the present invention.
  • the build up of static charges and subsequent dust attraction and/or sparking e.g. during loading of films in cassettes, e.g. X-ray cassettes, or transport in cameras, e.g. micro-film cameras, and projectors, can be avoided.
  • antistatic layer/barrier layer assemblage is particularly useful in reducing the surface resistance of photographic silver halide emulsion materials it is likewise useful in reducing surface resistance of photographic materials based on diazo-type compositions, vesicular-image forming materials, magnetic recording materials, electrographic or electrophotographic recording materials and mounting or drafting film.
  • the 3,4-disubstituted thiophenes of the formula (II) can be obtained by processes known in principle by reacting the alkali metal salts of 3,4-dihydroxy-thiophene-2,5-dicarboxylic esters with the appropriate alkylene vic-dihalides and subsequently decarboxylating the free 3,4-(alkylene-vic-dioxy)thiophene-2,5-dicarboxylic acids (see, for example, Tetrahedron 1967 Vol. 23, 2437-2441 and J. Am. Chem. Soc. 67 (1945) 2217-2218).
  • a longitudinally stretched polyethylene terephthalate support having a thickness of 0.1 mm was subbed with a terpolymer latex of vinylidene chloride/methyl acrylate/itaconic acid (88/10/2) and colloidal silica (surface area 100 m 2 /g). After stretching in the transverse direction the coverages of said terpolymer and of said silica in said subbing layer were 170 mg/m 2 and 40 mg/m 2 respectively.
  • an antistatic layer was applied from a mixture of 140 ml of the above prepared poly(3,4-ethylenedioxythiophene) dispersion, 858 ml of water and 2 ml of a 5 % solution in water of wetting agent AKYPO OP 80 (tradename).
  • the coating proceeded at a wet coverage of 50 m 2 /l resulting after drying at 115 °C in a dry solids coverage of 70 mg/m 2 .
  • a barrier layer was coated at a solids coverage of 0.5 g/m 2 from an aqueous dispersion (latex) of a terpolymer of vinylidene/methyl methacrylate/itaconic acid (88/10/2).
  • the surface resistance was measured according to test procedure A as defined herein at 30% and 60% relative humidity (RH) conditions and temperature of 21 °C.
  • the results expressed in ohm/square are listed in the following Table 1.
  • the adherence of the barrier layer to the underlying antistatic layer was tested in dry state and after pre-wetting by immersion for 10 minutes in water of 38 °C.
  • Example 1 was repeated with the difference however that onto said barrier layer a gelatin-containing layer supressing the tendency to curl of photographic gelatin-silver halide emulsion layer materials was coated.
  • the coating of the anticurl layer proceeded in such a way that gelatin and colloidal silica (surface area 300 m 2 /g) were present at a dry coverage of 2.5 g/m 2 and 1.2 g/m 2 respectively.
  • 20 ml/l of an aqueous coating solution (4.8 g/100 ml) of dimethylol urea having a concentration of 4.8 g/100 ml were added.
  • As wetting agent 10 ml/l of ULTRAVON W (trade name for the disodium salt of 2-heptadecylbenzimidazole disulphonic acid sold by CIBA A.G. Switserland) was added.
  • Example 2 As in Example 1 the surface resistance and charge mobility were measured. The results are listed in the following Table 2.
  • the optical density of the layer assemblage (1) containing said antistatic layer and said barrier layer and of the layer assemblage (2) containing the assemblage (1) in conjunction with said anticurl layer measured with Macbeth TD 904 densitometer are mentioned also in said Table 2.
  • the optical density measurements proceeded before processing (BP) in the UV (at 370 nm) and wavelength range (350-630 nm).
  • Example 2 was repeated with the difference however that the described barrier layer was omitted and the gelatin-containing layer supressing the tendency to curl was coated directly onto the antistatic layer.
  • Example 2 As in Example 1 the resistance applying test procedures A and B, and the adherence were measured.
  • the surface resistance and RC-time results are listed in the following Table 3.
  • a subbed polyethylene terephthalate support as described in Example 1 was coated with an antistatic layer from the above prepared poly(3,4-ethylenedioxy-thiophene) dispersion (1) of which 88 ml were used in admixture with 912 ml of water.
  • the coating proceeded at a wet coverage of 60 m 2 /l and the coated layer was dried at 120 °C. A transparent and practically colourless antistatic layer was obtained.
  • the surface resistance was measured before processing (BP) at 21 °C in relative humidity circumstances of 30 %.
  • Comparative Example 2 was repeated with the difference however that onto said antistatic layer first a barrier layer was coated having in addition to the composition of Example 1 10 % by weight of ethylene carbonate calculated on its latex polymer content. Onto said barrier layer an anticurl layer as defined in Example 2 was coated. The coverages of solids of the barrier layers in the Examples 3 to 5 were 1, 1.8 and 2.6 g/m 2 respectively.
  • Example 2 the surface resistance and discharging time were measured at 30% relative humidity and 21 °C before (BP) and after (AP) wet processing as applied in silver halide photography. The results are presented in the following Table 5. As in Example 2, the optical density of the layer assemblage including the anticurl layer was determined.
  • Example 1 material Onto the barrier layer of the Example 1 material a gelatin-silver bromide-iodide emulsion [AgBr/AgI (99/1 mole %] was coated at a coverage of silver halide equivalent with 2.06 g of silver nitrate per m2. The gelatin to silver halide ratio was 1.5, the silver halide being expressed as an equivalent amount of silver nitrate. The average grain size of the silver halide was 0.35 ⁇ m.

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Claims (11)

  1. Matériau en feuille ou en bande comprenant un support en résine hydrophobe ou un support en papier recouvert d'au moins une couche de résine hydrophobe, dans lequel ledit support en résine ou ladite couche de résine est recouvert d'une couche antistatique transparente contenant, à titre de composant essentiel, un polythiophène polymérisé par oxydation comprenant un squelette polymère conjugué en présence d'un composé de polyanion polymère, caractérisé en ce que ladite couche antistatique est recouverte d'une couche d'arrêt adhérente de recouvrement appliquée à partir d'une dispersion polymère aqueuse, c'est-à-dire un latex polymère, dans lequel ledit polymère possède une fonctionnalité hydrophile suffisante pour faire en sorte que ladite couche de recouvrement adhère à la couche contenant un colloïde hydrophile qui la recouvre.
  2. Matériau en feuille ou en bande selon la revendication 1, dans lequel ladite couche d'arrêt est recouverte d'une couche contenant un colloïde hydrophile.
  3. Matériau en feuille ou en bande selon la revendication 2, dans lequel ladite couche contenant un colloïde hydrophile est une couche d'émulsion au gélatinohalogénure d'argent ou une couche de support dudit matériau, contenant de la gélatine.
  4. Matériau en feuille ou en bande selon l'une quelconque des revendications 1 à 3, dans lequel lesdits polythiophènes à utiliser conformément à la présente invention sont constitués d'unités de structure répondant à la formule générale (I) ci-après : dans laquelle
    chacun des radicaux R1 et R2 représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe alkyle en C1 - C4 ou bien, représentent ensemble, un groupe alkylène en C1 - C4 le cas échéant substitué.
  5. Matériau en feuille ou en bande selon l'une quelconque des revendications 1 à 3, dans lequel on prépare ledit polythiophène en présence dudit composé de polyanion polymère par polymérisation par oxydation de 3,4-dialcoxythiophènes ou de 3,4-alkylènedioxythiophènes répondant à la formule générale (II) ci-après : dans laquelle
    R1 et R2 sont tels que définis à la revendication 3.
  6. Matériau en feuille ou en bande selon l'une quelconque des revendications 1 à 5, dans lequel ledit composé de polyanion polymère est un acide carboxylique polymère ou un acide sulfonique polymère ou encore un tel acide sous forme neutralisée.
  7. Matériau en feuille ou en bande selon la revendication 6, dans lequel ledit composé de polyanion polymère est un polymère comprenant des unités d'acide styrène-sulfonique.
  8. Matériau en feuille ou en bande selon l'une quelconque des revendications précédentes, dans lequel ledit polymère dans la couche d'arrêt est un copolymère de (1) un ou plusieurs monomères polymérisables choisis parmi le groupe constitué par le styrène, le chlorure de vinylidène, l'acrylonitrile, des acrylates d'alkyle et des méthacrylates d'alkyle avec (2) un ou plusieurs comonomères polymérisables substitués choisis parmi le groupe constitué par des styrènes, des acrylates d'alkyle et des méthacrylates d'alkyle qui portent, à titre de substituants, un groupe de sel d'aminoalkyle, un groupe hydroxyalkyle ou encore un groupe d'acide carboxylique.
  9. Matériau en feuille ou en bande selon la revendication 8, dans lequel le groupe de monomères (1) est constitué par l'acrylate d'éthyle, le méthacrylate d'éthyle, l'acrylate de butyle et le méthacrylate de butyle et le groupe de monomères (2) est constitué par le chlorhydrate du méthacrylate de 2-aminoéthyle, l'acrylate de 2-hydroxyéthyle, le méthacrylate de 2-hydroxyéthyle, le chlorhydrate du N-(3-aminopropyl)-méthacrylate, l'acide acrylique du chlorhydrate de p-aminostyrène et l'acide itaconique.
  10. Matériau en feuille ou en bande selon la revendication 8, dans lequel le polymère présent dans ladite couche d'arrêt est un copolymère contenant des unités de structure de vinylidène à concurrence d'au moins 50 moles % et des unités de structure contenant des groupes carboxy fonctionnels.
  11. Matériau en feuille ou en bande selon l'une quelconque des revendications précédentes, dans lequel ledit matériau est un matériau photographique contenant une couche d'émulsion à l'halogénure d'argent.
EP92204062A 1992-01-28 1992-12-23 Matériau en feuille ou bande avec des propriétés antistatiques Expired - Lifetime EP0554588B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP92204062A EP0554588B1 (fr) 1992-01-28 1992-12-23 Matériau en feuille ou bande avec des propriétés antistatiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP92200230 1992-01-28
EP19920200230 EP0553502A1 (fr) 1989-04-27 1992-01-28 Matériau en feuille ou en bande ayant des propriétés antistatiques
EP92204062A EP0554588B1 (fr) 1992-01-28 1992-12-23 Matériau en feuille ou bande avec des propriétés antistatiques

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EP0554588A1 EP0554588A1 (fr) 1993-08-11
EP0554588B1 true EP0554588B1 (fr) 2004-03-31

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4334390C2 (de) * 1993-10-08 1999-01-21 Nat Science Council Verfahren zur Herstellung eines verarbeitbaren, leitfähigen, kolloidalen Polymeren
EP0695789B1 (fr) * 1994-08-01 2002-02-27 Hitachi Maxell Ltd. Feuille d'impression dont les dépôts peuvent être enlevés aisement
US5529884A (en) 1994-12-09 1996-06-25 Eastman Kodak Company Backing layer for laser ablative imaging
EP1031875A1 (fr) * 1999-02-22 2000-08-30 Agfa-Gevaert N.V. Matériau radiographique à l'halogénure d'argent sensible à la lumière ayant des propriétés antistatiques satisfaisantes pendant sa manipulation
US6077655A (en) † 1999-03-25 2000-06-20 Eastman Kodak Company Antistatic layer for imaging element containing electrically conductive polymer and modified gelatin
US6692662B2 (en) * 2001-02-16 2004-02-17 Elecon, Inc. Compositions produced by solvent exchange methods and uses thereof
EP2105458A1 (fr) 2008-03-27 2009-09-30 Agfa-Gevaert Composition polythiophène apte à la dispersion

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006451A (en) * 1989-08-10 1991-04-09 Eastman Kodak Company Photographic support material comprising an antistatic layer and a barrier layer
EP0440957B1 (fr) * 1990-02-08 1996-03-27 Bayer Ag Dispersions de polythiophènes nouvelles, leur préparation et leur utilisation

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Publication number Publication date
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